Complex amido-substituted esters of beta-phosphato-alpha, beta-olefinically unsaturated monocarboxylic acids



United States Patent COMPLEX AMIDO-SUBSTITUTED ESTERS F BETA-PHOSPHATO-ALPHA, BETA-OLEFINI- CALLY UNSATURATED MONOCARBOX- YLIC ACIDS Alan R. Stiles and Richard R. Whetstone, Denver, Colo,

assignors to Shel! Development Company, New York, Y., a corporation of Delaware No Drawing. Application December 28, 1955 Serial No. 555,757

4 Claims. (Cl. 260-461) are esters of beta-phosphato-alpha,beta-olefinically unsaturated monocarboxylic acids represented by the formula if i F i (R0)2P0C=COOH wherein R represents a represents the hydrogen atom or a hydrocarbon radical, with It is preferred that R be an alkyl group, the lower alkyl groups, particularly those containing 8 carbon atoms or less each, being the most desirable members of this preferred group.

The symbol R represents the same hydrocarbon groups as are designated by the symbol R The symbol R preferably represents an alkylene group, and most desirably a lower alkylene group-i. groups containing up to about eight carbon atoms. The group represented by R may be of either branchedchain or straight-chain configuration. The linking valence bonds of the group R may be on the same or on different carbon atoms.

wherein A is a monovalent acid group and B is a hydrogen atom, a hydrocarbyl group or such a monovalent acid e., alkylene 2,865,944 Patented Dec. 23, 1958 group as is represented by A. of amides of carboxylic acids wherein R Included are. the residues (A and/or B=C(O)R is a hydrocarbyi group), such as the residues its R derivatives and esters (e. g., amido groups derived from the urethanes), including the aliphatic thioar'nides (A and/or B=+C(S)R including thiourea. Also included are the residues of amides of aromatic acids, such as the residue of benzamide, l-naphthamide, phthalimide, and the like. Also included are the amides of sulfonic acids (A and/or B=SO R including sulfamic acids and its R derivatives and esters and the like, and derivatives of sulfamide, and its R derivatives, the amides of and the phosphinamides [A and/or B= P(O)(R (R the sulfur and other acids.

of the said subgenus having the structure i N-CR wherein R and R have their previously stated meanings.

Examples of this new class of compounds include:

2-(2-acetamidoethoxycarbonyl) 1 methylvinyl dimethyl phosphate 2-(2-acetamidoethoxycarbonyl) l methylvinyl diethyl phosphate 2-(2-propionamidoethoxycarbonyl) 1,2 dimethylvinyl dimethyl phosphate- 2-(2-benzenesulfonamidoethoxycarbonyl) vinyl diethyl phosphate 2 (2 dimethylphosphoramido ethoxycarbonyl) lmethylvinyl dimethyl phosphate 2-(Z-caproamidoethoxycarbonyl)-ethenyl diethyl phate 2-(2-acetamidopropoxycarbonyl)-1-phenylviny1 dipropyl phosphate 2-(Z-diacetamidoethoxycarbonyl) vinyl dimethyl phosphate 2-[3-(N-ethylacetamido)-propoxycarbonyl] 1 vinyl dibutyl phosphate 2-(2-benzamidoethoxycarbonyl)-1-methylvinyl dimethyl phosphate Compounds of this preferred subgenus in which each of the groups, R, R R and R contains no more than eight carbon atoms have been found to be highly active insecticides with excellent residual activity.

These new compounds are conveniently prepared by (a) the reaction of an amide alcohol B and diketene or a substituted diketene to form the corresponding beta-oxo acid amide, according to the equation R1CH=?-O A'\ 1 methylphos- 1 methyl 2 ethylmethyl- The reaction 'is catalyzed by acidic or basic catalysts, supl; as acidic or basic resins, tertiary amines, or sulfonic ac1 s.

The reaction is conveniently conducted by slowly adding the diketene to a mixture of the amido alcohol and the catalyst, heating or cooling as necessary to maintain a moderately elevated temperature (80 C. to 125 C. is usually most satisfactory). The reaction mixture temperature is maintained for a short. time-e. g., fifteen minutes to an hour-after all of the diketene has been added to insure complete reaction. The product is recovered by distillation.

- (b) Reaction of the product of (a) with sulfuryl chlorrde to give the 2-chloro-substituted compound Reaction (b) is carried out according to the method described by Dey in Journal of the Chemical Society, volume 107 (1915) at page 1646 et seq., by McBeth in Journal of the Chemical Society, volume 123, page 1125 et seq. (1925), and by Allihn, Berichte der deutschen Chemischen Gesellschaft, volume 11, page 567 et seq. (1878).

Reaction of the Z-chloro-substituted compound with a phosphite, (R0) P, to give the desired products.

The phosphites are a well known class of compounds, ordinarily prepared by reacting one mole of phosphorus trichloride with three moles of an alcohol or phenol in the presence of three moles of a basic hydrogen chloride acceptor (Kosolapolf, Organic-Phosphorus Compounds, Wiley (1950) pages 184 and 185).

7 Reaction (c) is carried out by adding about an equimolar amount of the phosphite to the chloroester, the addition usually being made slowly so as to avoid undue temperature increase of the reaction mixture from the exothermic heat of reaction. The reaction may be started with the reactants at an ordinary temperature of about 20 to 25 C., but for the most part is conducted at a temperature between about 60 C. and 150 C. In some cases, the starting of the reaction is assisted by application of heat, and especially if large quantities of reactants are used, cooling is employed to control the temperature within the desired range. The formed alkyl chloride is preferably removed from the reaction mixture to greater or lesser extent by application of suflicient vacuum so that chloride is boiled out. When the boiling points of the formed alkyl chloride and the chloroester reactant are fairly close together, use of a distillation columnfor removal of the alkyl chloride is advisable for best results. Some of the higher reactants are solids at ordinary temperature, but use of an inert solvent such as xylene enables a fluid reaction system to be realized. The reaction is effected under substantially anhydrous conditions. In order to insure completion of the reaction after addition of the chloroester, the reaction mixture is heated within the indicated temperature range for a reasonable time. The formed phosphate is usually recovered by distillation under sufiiciently low pressure that thermal decomposition is avoided. If desired, especially with higher compounds of the invention, crystallization or molecular distillation may be used for recovery of the phosphates.

Preparation of a typical, but non-limiting member of the new class of compounds is described in detail in the following example:

EXAMPLE I Reaction of diketene with an amino alcohol sion of the addition, heat is applied to maintain the temperature at to C. for an additional V2 hour. The product, 2-acetamidoethyl acetoacetate, is then obtained by a very high vacuum distillation (molecular still) as a viscous liquid (213 grams-75% of theory). B. P. l50-160 C. (0.001 mm), 11 1.4700. (Nitrogen; found 7.5%; calculated 7.5%.)

Reaction of sulfuryl chloride with acetoacetate Sulfuryl chloride (138 grams-1.02 moles) is added at 10 to 20 C.- to Z-acetamidoethyl acetoacetate (191 grams-102 moles) in 100 ml. benzene over a period of two hours. Cooling is required. After addition iscompleted, the mixture is heated at 50 C. and 40 mm. for one hour to remove the by-product gases. The product is isolated by a high vacuum distillation (molecular still). Yield 184 grams (81.5% of theory). B. 1 C. (0.001 mm.).

Z-acetamidoethyl Calculated for Found NOgCsHmCl 2-(Z-actamidoethoxycarbonyl)-1-methylvinyl dimethyl phosphate is prepared by the following procedure: Tllmethyl phosphite (106 grams-0.855 mole) is added over a one-hour period to Z-actamidoethyl 2-chloroacetoacetate (182 grams-0.825 mole) at about 80 to 95 C. The reaction is moderately exothermic. At the conclusion of the addition, heat is applied to maintain the temperature at 95 to 105 C. for an additional two hours. During the last hour a vacuum of 55 to 85 mm. is applied to remove the by-product methyl chloride. The product 18 obtained fairly pure by a high vacuum distillation (molecular still). B. P. 175 to 80 C. (0.001 mm); n D 1.4785. Yield grams, 65.8% of theory.

Many of the complex esters of the invention are liquids at ordinary temperatures of 20 C. to 25 C. although higher members are crystalline solids at such normal temperatures. The new compounds are very useful substances for a variety of applications, but are of particular utility as insecticides because they possess outstanding properties when employed as contact and stomach poisons. The compounds are highly toxic to insects, a term which is employed herein to include not only members of the class Insecta, but also related or similar non-vertebrate animal organisms belonging to the allied classes of arthropods and including mites, ticks, spiders, wood lice, and the like.

The compounds of this invention can be employed for insecticidal purposes by the use of any of the methods which are conventionally employed in that art. For example, the compounds can either be sprayed or otherwise applied in the form of a solution or dispersion, or they can be absorbed on an inert, finely divided solid and applied as a dust. Useful solutions for application by spraying, brushing, dipping, and the like, can be prepared by using as the solvent any of the well-known inert horticultural carriers, including neutral hydrocarbons such as kerosene and other light mineral oil distillates of intermediate viscosity and volatility. Adiuvants, such as spreading or wetting agents, can also be included in the solutions, representative materials of this character being fatty acid soaps, rosin salts, saponins, gelatin, casein. long chain fatty alcohols, alkyl aryl sulfonates, long-chain upon the total weight some ployed in conjunction with other insecticidally-active Representative insecticides of this latter class include the naturally-occurring insecticides such as rethrum, rotenone, sabedilla, and the like, as well as hexachloride, thiodiphenylamine, cyanides, tetraethyl pyrophosphate, diethyl-p-nitrophenyl thio-phosphate, azobenzene and the various compounds of arsenic, lead, and/ or fluorine.

The following examples demonstrate the insecticidal EXAMPLE II (:1) parathion, (b) nicotine, (c) the gamma isomer of hexachlorobenzene, all insecticides Widely used was the same.

The toxicities are expressed in terms of the relation ship between the amount of standard insecticide required to produce 50% mortality of the test insects and the amount of the test material required to produce the same mortality. Assigning the standard insecticide an arbitrary rating of 100%, the toxicity of the test materials is expressed in terms of the toxicity index which compares the activity on a percentage basis with that of the standard insecticide. The results are shown in the following table:

eases-4a TABLE I Mexican Two- Hy- Test Insect Pea aphid been spotted drengea bettle spider mite larva mite Gamma Standard Inseoticide Para- Nico- Benzene Para- Parathion tine Hexathion thion chloride Compound: 2-(2-acetomidoethoxycarbonyl)-1-methyl vinyl dimethyl phosphate 170 6,250 760 730 260 EXAMPLE III 2-(2-acetamidoethoxycarbonyl)-l-methylvinyl dimethyl phosphate (hereinafter designated as compound A), a representative compound of the invention, was tested to determine its residual toxicity with respect to the adults equally infested test plants), the count being made 24 hours after the infestation. The details of the tests and the results thereof are summarized in the following tables:

TABLE II [Test insect: Onion thrips Tlmps tabaci).]

Percent Control Concentration of active material in spray as 021/100 3 oz./100 gal. 6 oz./l00 gal.

Time (infe)station after spraymg, day 1 7 1 7 1 7 83 53 83 78 92 81 Systox (comparison) 69 42 64 60 TABLE III [Test insect: Hydrangea mite. Test compound: A concentration of active material in spray: 4 oz./10O gaL] Time (infestation after spraying, days) 1 2 7 Percent control TAB LE IV [Test insect: Adult two-spotted spider mite.]

Percent Control Concentration of active material in spray 1.0% 0.25%

Time (infestation after spraying, days) 1 7 1 7 Compound:

TABLE V Test insect: Me ican bean bettle larva.

Time of infestation: 7 days after spraying.

At a concentration of 0.035% w., compound A killed 77% of the test insects When the test plants were kept in the sun. At a concentration of 0.05% W., Parathion killed 50% of the insects under shady conditions and 2% of the insects under sunny conditions.

Systox under conditions such. that the residual toxicity of the compounds toward the eggs, and the young hatched from the eggs, as well as the adults or two-spotted spider mites, would be measured. The time of infestation was 7 days after spraying. The results are: shown in the following table: (In the table, the concentration of the test compound in the spray is given in parentheses following the percent kill.)

TABLE VI Compound Percent Kill A 99 0.02%) 100 (0.04%) 100 (0. 08%) Parathlon 50 0. 15%) 70 (0. 3%) 88 (0.6 Systox 83 (0. 06%) 86 (0. 12%) 9B (0. 24%) Under the same conditions, dimethyl l-carbomethoxyl-propen-Z-yl phosphate, '3. known insecticide, killed but 59% of the insects at a concentration of 0.09% and but 78% of the insects at a concentration of 0.18%.

EXAMPLE V TABLE VII 7 Percent Control We claim as our invention: 1. A compound of the formula R R o R 0 II I l H I ll (RO)aP-0C=C-C0R -NCR wherein R represents an aliphatic hydrocarbon radical of l to 8 carbon atoms, R represents a member of the group consisting of the hydrogen atom and alkyl radicals of l to 8 carbon atoms and R represents a lower alkylene radical.

2. A compound of the formula 0 R R 0 R 0 H l I I! l l (ROMP-O-C: c-0- '--N R wherein R represents an aliphatic hydrocarbon radical of 1 to 8 carbon atoms, R represents hydrogen and R represents a lower alkylene radical. '5. A compound of the formula R B o R 0 II I I ll I l (ROMP-0C=C-CO-B.1N0-R wherein R represents an aliphatic hydrocarbon radical of l to 8 carbon atoms, R represents an alkyl radical r of 1 to 8 carbon atoms and R represents a lower alkylene radical.

4. 2 (2 acetamidoethoxycarbonyl)-l methylvinyl di-- methyl phosphate.

No references cited. 

1. A COMPOUND OF THE FORMULA 